Microbial fuel cells for bioelectricity generation through reduction of hexavalent chromium in wastewater: A review

The study proposes the use of microbial fuel cell (MFC) technology to reduce toxic Cr(VI) present in industrial wastewater to less toxic trivalent chromium [Cr(III)], while generating electricity through a bioelectrochemical oxidation-reduction process. Factors influencing the treatment process and electricity generation include the concentration of Cr(VI) in wastewater, substrate types used for anodes, types of microorganisms involved, types of cathode and anode, surface area of the cathode and anode, and pH and temperature of cathodic and anodic solutions. While other heavy metals in wastewater may be removed by MFC technology, Cr(VI) removal is more efficient in terms of electricity generation. Previous research indicated that the maximum electrical power generated by Cr(VI) removal through the use of MFCs is 1600 mW/m², which is expected to increase as the factors affecting this process are optimized. Based on current data, MFC-based electricity generation along with Cr(VI) removal is a potential future source of sustainable energy. However, research priorities need to focus on reducing the cost of MFC technology by using economical and effective materials and increasing electricity production.     

Development of an ambient temperature alkaline electrolyser for dynamic operation with renewable energy sources

A comparison is made between the ambient and conventional temperature alkaline electrolysers in terms of operational system, voltage efficiency and corrosion rates. The capital, operational and maintenance costs are reduced by reducing auxiliary equipment as well as auxiliary utilities in the ambient temperature alkaline electrolyser. Also, since auxiliary electricity consumption is reduced, the alkaline electrolyser is capable for dynamic, continuous and fast-response operation with renewable energy sources. The ambient temperature alkaline electrolyser is capable for wider operational range and faster response time when powered by wind energy sources. Although the voltage efficiency for hydrogen production is increased by about 12% at the conventional operating temperature, corrosion rate of the electrode is increased by a factor of about 6.3. The voltage efficiency for hydrogen production, however, is increased by about 12% by employing electrocatalyst in the ambient temperature alkaline electrolyser, and there is benefit of enhancing lifetime durability of the electrode as well as cell components at relatively lower operating temperature.     

Influence of CeO2 nanoparticles in the stability of electrodeposited Ni anodes for alkaline electrolysers

In Mexico, the National Electric System Development Program (PRODESEN 2022–2036) establishes the use of green hydrogen to be supplied in Combined Cycle Power Plants in a mixture of 70% CH₄ and 30% H₂ for electric energy generation. For those places where natural resources such as sun, wind, and water are available, the best option is to use alkaline electrolysers due to cost and lifetime. The oxygen evolution reaction (OER), which takes place at the anode, is the limiting factor in the performance of an alkaline electrolyser because large overpotentials are required to break the (O–H)^- bond needed to form the double bond of the gaseous oxygen molecule (OO). Many studies under the initial research stage report using Ni–CeO₂ as a promising catalyst toward OER, observing good catalytic activity and stability at low overpotentials. This work deposited electrodes with Ni and Ni–CeO₂ films of 80 μm on AISI 304 Stainless steel substrates.A kinetic study was performed using linear sweep voltammetry to determine the Tafel slope of the OER. An electrolysis system was integrated with these anodic electrodes and tested for 500 h to determine the stability of films at real operating conditions using 15 wt% NaOH as electrolyte @ 0.5 A cm⁻². A better OER activity of the modified Ni–CeO₂ electrodes than Ni electrodes was obtained. Ni–CeO₂ electrode shows an onset potential of 1.48 V, a potential of 1.56 V at 5 mA cm⁻², and a Tafel slope of 75.71 mV dec⁻¹, which is related to a reaction determining step in an oxidation process of (OH)⁻ via the one-electron transfer to the surface which is partial cover by OH species adsorbed. In the studies with the electrolyser test system, the Ni electrodes with an electrodeposited film of 80 μm showed good stability, and the film remained on the surface electrode.On the other hand, the electrode modified with Ni–CeO₂ showed instability and high overpotentials as 500 h were completed. The last is attributed to the low conductivity of CeO₂ and the formation of the passive NiO/NiOH₂ layer on the electrode surface, which is not easily detached due to the presence of CeO₂. These results confirm the importance of conducting tests in an electrolyser under real conditions.     

Influence of process conditions on gas purity in alkaline water electrolysis

In this paper the influence of operating conditions on the product gas purity of a zero-gap alkaline water electrolyzer was examined. Precise knowledge of the resulting gas purity is of special importance to prevent safety shutdown when the electrolyzer is dynamically operated using a renewable energy source. The investigation in this study involves variation of temperature, electrolyte concentration and flow rate as well as different electrolyte management concepts. The experiments were carried out in a fully automated lab-scale electrolyzer with a 150 cm² zero-gap cell and approximately 31 wt% KOH at ambient and balanced cathodic and anodic pressure. The purity of the evolved gases was measured via online gas chromatography. It can be seen from the experiments that a temperature increase and flow rate decrease reduces the gas impurity when mixing catholyte and anolyte. A further reduction of gas impurity can be achieved when both cycles are being separated and a dynamic cycling strategy is applied.     

Influence of the power supply on the energy efficiency of an alkaline water electrolyser

Electric energy consumption represents the greatest part of the cost of the hydrogen produced by water electrolysis. An effort is being carried out to reduce this electric consumption and improve the global efficiency of commercial electrolysers. Whereas relevant progresses are being achieved in cell stack configurations and electrodes performance, there are practically no studies on the effect of the electric power supply topology on the electrolyser energy efficiency. This paper presents an analysis on the energy consumption and efficiency of a 1 N m³ h⁻¹ commercial alkaline water electrolyser and their dependence on the power supply topology. The different topologies of power supplies are first summarised, analysed and classified into two groups: thyristor-based (ThPS) and transistor-based power supplies (TrPS). An Electrolyser Power Supply Emulator (EPSE) is then designed, developed and satisfactorily validated by means of simulation and experimental tests. With the EPSE, the electrolyser is characterised both obtaining its I–V curves for different temperatures and measuring the useful hydrogen production. The electrolyser is then supplied by means of two different emulated electric profiles that are characteristic of typical ThPS and TrPS. Results show that the cell stack energy consumption is up to 495 W h N m⁻³ lower when it is supplied by the TrPS, which means 10% greater in terms of efficiency.     

Hydrogen production from crude glycerol in an alkaline microbial electrolysis cell

Crude glycerol is an undesired by-product of biodiesel production with a low commercial value (i.e. a ton of biodiesel results in around 110 kg of crude glycerol) and, thus, glycerol needs valorization. In particular, there is a need of providing a benefit to alkaline wastewaters from biodiesel production with excess of glycerol. Bioelectrochemical systems (BES) are an emerging technique to recover the energy contained in a substrate either as electricity or as other added-value products such as hydrogen. Moreover, promising results have been reported with alkaline BES showing higher current intensities than neutral pH conditions. This study is the first experimental evaluation of alkaline bioelectrochemical production of hydrogen from real crude glycerol as sole carbon source. The results show that alkaline glycerol degradation is feasible under both microbial fuel cell mode (2 mA, 71.4 A/m³ and 55% of CE) and microbial electrolysis mode (maximum of 0.46 L_H2/L/d and 85% of r_CAT). The values obtained are promising since they are in the range of those obtained with other simpler carbon sources such acetate. A complex consortium involving fermentative bacteria (such as Enterococcaceae), alkaline exoelectrogens (such as Geoalkalibacter) and homoacetogens (such as Acetobacterium) was naturally developed in the anode of the MEC.     

Femtosecond laser molybdenum alloyed and enlarged nickel surfaces for the hydrogen evolution reaction in alkaline water electrolysis

A simple femtosecond laser alloying process is applied under two different process gases nitrogen and air to create novel molybdenum-nickel alloyed and surface enhanced catalysts. A three-day electrochemical test protocol is applied in an alkaline half-cell at 298 K and 353 K to examine the catalytic activity and initial degradation mechanisms in the hydrogen evolution reaction. It is found, that the surface enhancement and the stability of the electrode significantly depends on the process gas. Molybdenum is degraded at the beginning of the test protocol, but it is shown that higher concentrations are not necessarily required for an increase performance. The highest catalytic activity on an electrode alloyed with molybdenum under nitrogen emerges in a steady state operation at 353 K. An overpotential of 135 mV at ?100 mA cm^?2 is measured.     

Reducing the hydrogen production cost by operating alkaline electrolysis as a discontinuous process in the French market context

The possible reduction of the hydrogen production cost when operating alkaline electrolysers in a discontinuous way, in order to benefit from low electricity prices, is investigated. Beside the insights about the electricity market (prices do not correlate the demand; they are related to the supply-and-demand hardness), advances in modelling discontinuous operation are proposed. An optimum production cost is found that induces a profit of 4%, with regard to a plant that would work continuously. Specific attention should be given to related overcosts: additional degradation due to frequent transitions from the minimum electrolyser load to the nominal one, higher maintenance needs, and hydrogen storage costs. Such an operating mode would also greatly benefit from a reduction of the electrolyser prices. However, the state-of-the-art as regards the electrolyser minimum loads and transition time appears satisfactory.     

Ni/Fe electrodes prepared by electrodeposition method over different substrates for oxygen evolution reaction in alkaline medium

A series of Ni/Fe electrodes have been prepared by electrodeposition of metal salt precursors on different substrates. The surface morphology, chemical composition and electrochemical characteristics of these electrodes were studied by various physico-chemical techniques such as X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). The electrochemical properties of the electrodes were examined by steady-state polarization curves. First, the influence of features such as Ni/Fe composition and type of substrate for the oxygen evolution reaction (OER) were determined by electrochemical techniques in a conventional 3-electrodes cell. The overpotential for the OER is lower for the electrodes with the higher concentrations of Ni. The electrodes with a Ni/Fe composition of 75/25 wt.% electrodeposited on steel mesh and/or 75/25 and 50/50 wt.% on nickel foam result in the most active configurations for the OER. These electrodes were further tested as anodes for alkaline water electrolysis during at least 70 h. In order to understand their activity and stability, the used electrodes were also characterized by SEM and compared to the fresh electrodes. Among the compositions and substrates examined, the Ni50Fe50-Nf electrode exhibited the lowest overpotential (2.1 V) for the OER and the higher stability as anode in an alkaline water electrolysis cell.     

Aspen Plus model of an alkaline electrolysis system for hydrogen production

A model of an alkaline electrolysis plant is proposed in this paper, including both stack and balance of plant, with the objective of analyzing the performance of a complete electrolysis system. For this purpose, Aspen Plus has been used in this work due to its great potential and flexibility. Since this software does not include codes for modelling the electrolysis cells, a custom model for the stack has been integrated as a subroutine, using a tool called Aspen Custom Modeler. This stack model is based on semi-empirical equations which describe the voltage cell, Faraday efficiency and gas purity as a function of the current. The rest of the components in the electrolysis plant have been modelled with standard operation units included in Aspen Plus. Simulations have been carried out in order to evaluate and optimize the balance of the plant of an alkaline electrolysis system for hydrogen production. Also, a parametric study has been conducted. The results show that increasing the operation temperature and reducing the pressure can improve the overall performance of the system. The proposed model in this work for the alkaline electrolyzer can be used in the future to develop a useful tool to carry out techno-economic studies of alkaline electrolysis systems integrated with other process.     

Novel alkaline water electrolysis with nickel-iron gas diffusion electrode for oxygen evolution

In the present work, a novel electrolyzer concept for alkaline water electrolysis (AEL) with a gas diffusion electrode (GDE) as anode, a conventional immersed porous cathode and a state-of-the-art Zirfon™ separator is presented and compared with a conventional electrolyzer setup. Due to the utilization of a GDE in this configuration, the electrolyte is only circulated through the cathode compartment which greatly simplifies the process. The influence of the catalyst composition and the enhanced electrode surface owing to the three-dimensional porous structure of the GDE are characterized and investigated regarding the electrode performance. Furthermore, process parameters like contact pressure and differential pressure are examined and optimized. The novel process concept with a GDE as anode reveals a similar cell potential compared to a classical electrolysis cell with a Ni/Fe-coated nickel foam anode up to 400 mA cm⁻² at 353 K and 32.5 wt% KOH and also exhibits relatively good electrochemical stability over time.     

Dynamic modelling of an alkaline water electrolysis system and optimization of its operating parameters for hydrogen production

This work aims at developing an approach for modelling and optimizing the operation of a reference alkaline electrolysis unit operating in transient state using orthogonal collocation on finite elements (OCFE). The main goal is to define the set of operating conditions that minimize the processing cost (associated to electricity cost) given a hydrogen yield. Three components of the electrolyzer are considered: the stack of electrolytic cells and two separators that single out the hydrogen and oxygen gas streams. The dynamic behavior is considered for the mass holdup in the separators as well as the energy accumulation for these three components. The associated mathematical model is derived in the paper. Its solving allows characterizing the influence of the transient operating parameters of the system on its working and associated final hydrogen production. Mathematical optimization aims at defining the ideal operating load in order to minimize costs associated to fluctuating price of electricity consumed by the stack given a defined hydrogen yield. The model has been validated according to experimental test runs and operating conditions have been optimized under a proof of concept scenario saving 17% of electricity costs if compared to constant plant capacity.     

Electrochemically fabricated NiCu alloy catalysts for hydrogen production in alkaline water electrolysis

NiCu alloy catalysts for alkaline water electrolysis were prepared by an electrodeposition method varying the alloy composition. When the deposition potential became more positive, the bulk and surface Cu content in NiCu alloys as well as the catalyst particle size gradually increased, which were confirmed by various spectroscopic and electrochemical techniques. The surface coverage of the catalysts was found to be a function of the deposition potential, as well. The catalytic activities of the prepared NiCu alloys to hydrogen evolution reaction (HER) were investigated with cyclic voltammetry in a 6.0 M KOH electrolyte at 298 K, and the mass activities of NiCu alloys were correlated with bulk and surface Cu contents to investigate the Cu alloying effect.     

Electrocatalytic activity of simple and modified Fe-P electrodeposits for hydrogen evolution from alkaline media

Electrodeposition of Fe-P, Fe-P-Pt and Fe-P-Ce into copper substrates is carried out under galvanostatic conditions. The influence of the current density on the composition of the deposits and the current efficiencies for the electrodeposition processes are determined. Preliminary data indicate that addition of formic acid to the electroplating bath improves the current efficiency for electrodeposition. Electrocatalytic activities of the heat-treated plated materials are investigated by dc polarisation and ac impedance techniques for the hydrogen evolution reaction (HER) in 1 M NaOH solution at 298 K. Steady-state polarisation curves and electrochemical impedance spectroscopy data show that improved catalytic activities for the HER are due to an increase in the effective surface area, a change in surface features upon heat treatment, the partial contribution of the Pt component, and the electrocatalytic synergism with Fe imposed by the Ce co-deposit. Cathodic potentiostatic measurements for medium time operation indicate that the electroplated materials are stable even in moderately aggressive alkaline solutions.     

Microscopic high-speed video observation of oxygen bubble generation behavior and effects of anode electrode shape on OER performance in alkaline water electrolysis

An important difficulty associated with alkaline water electrolysis is the rise in anode overpotential attributable to bubble coverage of the electrode surface. For this study, a system with a high-speed video camera was developed, achieving in-situ observation of bubble generation on an electrode surface, monitoring an area of 1.02 mm² at 6000 frames per second. The relation between polarization curve (current density up to 3.0 A cm^?2) and oxygen bubble generation behavior on nickel electrodes having cylindrical wires and rectangular wires of different sizes (100–300 μm) was clarified. The generated bubbles slide upward, contacting the electrode surface and detaching at the top edge. Observations indicate that small electrodes have short bubble residence time and thin bubble covering layer on the electrode. As a result, the small electrode diameter contributes to smaller overpotential at high current density.     

A novel nickel electrode with gradient porosity distribution for alkaline water splitting

Electrodes with porous structures are widely used in commercial alkaline water splitting devices. By optimizing the porous structure, the efficiency of alkaline water splitting devices could be evidently promoted. In this work, nickel electrodes with gradient porosity distribution were designed and fabricated through selective laser melting. The effect of gradient porous distribution structure on electrochemical performance of Ni electrode was evaluated. The results showed that with small pores towards counter electrode the prepared Ni electrodes exhibits better anodic performance, and a better cathodic performance is observed with big pores towards the counter electrode. It was considered as joint effect of active specific area and mass transfer. Finally, by applying an electrolysis cell with optimized arrangement, an improvement of 14% electrolysis efficiency is achieved, which shows the potential of Ni electrodes with gradient porosity distribution to be applied in commercial application of hydrogen generation.     

Laser structured nickel-iron electrodes for oxygen evolution in alkaline water electrolysis

In the present work, the ultra-short pulse laser ablation method is applied to create novel surface alloys on NiFe electrodes for the oxygen evolution reaction (OER) in alkaline water electrolysis. The nickel-to-iron ratio in the alloy can be controlled with the ultra-short pulse laser ablation method by varying the thickness of electrochemically deposited iron layers onto the nickel mesh substrate. Besides the application of the additional catalyst, the laser treatment enhances the surface area and a defined micro- and submicrometer structure is created in a single step. The laser structured nickel-iron electrodes show a significantly lower overpotential of 249 mV than an electrochemically deposited Ni-NiFe alloy with 292 mV at 10 mA cm⁻², 298 K and 32.5 wt% KOH for the OER, although some loss of iron over time could not be prevented.     

Ultrathin MoS2 nanosheets in situ grown on rich defective Ni0.96S as heterojunction bifunctional electrocatalysts for alkaline water electrolysis

Developing earth-abundant and highly active bifunctional electrocatalysts are critical to advance sustainable hydrogen production via alkaline water electrolysis but still challenging. Herein, heterojunction hybrid of ultrathin molybdenum disulfide (MoS₂) nanosheets and non-stoichiometric nickel sulfide (Ni_0.96S) is in situ prepared via a facile one-step hydrothermal strategy, followed by annealing at 400 °C for 1 h. Microstructural analysis shows that the hybrid is composed of intimate heterojunction interfaces between Ni_0.96S and MoS₂ with exposed active edges provided by ultrathin MoS₂ nanosheets and rich defects provided by non-stoichiometric Ni_0.96S nanocrystals. As expected, it is evaluated as bifunctional electrocatalysts to produce both hydrogen and oxygen via water electrolysis with a hydrogen evolution reaction (HER) overpotential of 104 mV at 10 mA cm⁻² and an oxygen evolution reaction (OER) overpotential of 266 mV at 20 mA cm⁻² under alkaline conditions, outperforming most current noble-metal-free electrocatalysts. This work provides a simple strategy toward the rational design of novel heterojunction electrocatalysts which would be a promising candidate for electrochemical overall water splitting.     

Test of conductor and semiconductor electrocatalysts in high voltage alkaline electrolyzer as production media for green hydrogen

Despite the restricted success of conductor and semiconductor electrodes in solving hydrogen production problems, they provide a promising alternative to expensive conventional electrodes in water electrolysis investigations. Titanium dioxide (TiO₂) and silver (Ag) are widely used as photocatalysts in water splitting systems for hydrogen generation. Though TiO₂ is an inactive chemical semiconductor with poor conductivity, it has not been entirely investigated as an electrocatalyst yet. Two criteria were used to achieve this target: supplying high voltage to overcome the TiO₂ large band gap and immersing it in an alkaline solution to activate its inert surface. For comparison study, Ag noble metal nanoparticles coating was employed as a competitive electrocatalyst. In this regard, the application of Ag and TiO₂ coated on Ti electrodes in a hydrogen production system operated under high voltage was reported. The nanoparticles were synthesized using cost-effective and simple methods based on UV-deposition for Ag nanoparticles and the chemical precipitation method for TiO₂ nanoparticles. Then the synthesized nanoparticles were deposited on the Ti electrodes by simple immersion. The synthesized nanoparticles and coated electrodes were tested by XRD, SEM, and EDS to study their morphology, structure, particle size, and surface composition. Based on these results, TiO₂ nano-powder and coated electrodes exhibited homogenous spheres with a mixture of rutile and anatase phases, the majority being the anatase phase. The Ag-coated Ti substrate possessed a smaller crystallite size compared to TiO₂ coated substrate. To evaluate the performance of Ag/Ti and TiO₂/Ti electrodes toward hydrogen production, H₂ flow rates were measured in a 3.6 M KOH electrolytic solution at 6 V. Hydrogen flow rates obtained for pure Ti, Ag, and TiO₂ electrodes at a steady state were 21, 35, and 37 SCCM (standard cm³/min), respectively. Also, it was found that energy consumption was reduced when the electrodes were coated with nanoparticles. Furthermore, the electrolyzer's performance was assessed by calculating the hydrogen production efficiency and the voltage efficiency. The results showed that using TiO₂ electrodes gave the best hydrogen production and voltage efficiencies of 27% and 23%, respectively. This study brings new insights about Ag and TiO₂ coated electrodes in alkaline water electrolysis at high voltage regarding nanoparticle performance, hydrogen production, system performance, and energy consumption. In addition, minimizing the fabrication and operation costs of hydrogen production is the major enabler for the broad commercialization of water electrolysis devices.     

Super-hydrophilic/super-aerophobic Ni2P/Co(PO3)2 heterostructure for high-efficiency and durable hydrogen evolution electrocatalysis at large current density in alkaline fresh water,alkaline seawater and industrial wastewater

Seawater electrolysis has become an efficient method which makes full use of natural resources to produce hydrogen. However, it suffers high energy cost and chloride corrosion. Herein, we first present a Ni₂P/Co(PO₃)₂/NF heterostructure in which Co(PO₃)₂ with the nano-rose morphology in-situ grown on the rough Ni₂P/NF. The unique 3D nano-rose structure and the optimized electronic structure of the heterostructure enable Ni₂P/Co(PO₃)₂/NF super-hydrophilic and super-aerophobic characteristics, and highly facilitate hydrogen evolution reaction (HER) kinetics in alkaline fresh water, alkaline seawater and even industrial wastewater at large current density, which is rarely reported. Significantly, at large current densities, Ni₂P/Co(PO₃)₂/NF only requires overpotentials of 217 and 307 mV for HER to achieve 1000 mA cm⁻² in alkaline fresh water and alkaline seawater, respectively, and requires an overpotential of 469 mV for HER to deliver 500 mA cm⁻² in industrial wastewater. Furthermore, the overall seawater splitting system in the two-electrode electrolyzer only requires voltage of 1.98 V to drive 1000 mA cm⁻², which also demonstrates significant durability to keep 600 mA cm⁻² for at least 60 h. This study opens a new avenue of designing high efficiency electrocatalysts for hydrogen production at large current densities in alkaline seawater and industrial wastewater.